I. Introduction
This invention relates to new light-sensitive materials for photoresist compositions. More particularly, this, invention relates to new photoactive compounds suitable for use as a photoresist alone or admixed with other compounds in a photoresist composition. The photoactive compounds of the invention are esterification products of aromatic novolak resins with o-quinone diazide sulfonyl compounds.
II. Description of the Prior Art
Photoresist compositions are well known in the art and described in numerous publications including DeForest, Photoresist Materials and Processes, McGraw-Hill Book Company, New York, 1975. Photoresists comprise coatings produced from solution or applied as a dry film which, when exposed to light of the proper wavelength, are chemically altered in their solubility to certain solvents (developers). Two types are known. The negative-acting resist is initially a mixture which is soluble in its developer, but following exposure to activating radiation, becomes insoluble in developer thereby defining a latent image. Positive-acting photoresists work in the opposite fashion, light exposure making the resist soluble in developer.
Positive-working photoresists are more expensive than negative-working photoresists but are capable of providing superior image resolution. For example, the positive-working photoresist described above can be developed to yield relief images with a line width as low as one micron or less. In addition, considering the cross-section of a photoresist image, the channels formed in the photoresist by development have square corners and sidewalls with only minimal taper.
The positive-working photoresists typically comprise a light-sensitive compound in a film-forming polymer binder. The light-sensitive compounds, or sensitizers as they are often called, most frequently used are esters and amides formed from o-quinone diazide sulfonic and carboxylic acids. These esters and amides are well known in the art and are described by DeForest, supra, pp. 47-55., incorporated herein by reference. These light-sensitive compounds, and the methods used to make the same are all well documented and described in prior patents including German Patent No. 865,140 granted Feb. 2, 1953 and U.S. Pat. Nos. 2,767,092; 3,046,110; 3,046,112; 3,046,119; 3,046,121; 3,046,122; and 3,106,465, all incorporated herein by reference. Sulfonic amide sensitizers that have been used in the formulation of positive-acting photoresists are shown in U.S. Pat. No. 3,637,384, also incorporated herein by reference. These materials are formed by the reaction of a suitable diazide of an aromatic sulfonyl chloride with an appropriate resin amine. Methods for the manufacture of these sensitizers and examples of the same are shown in U.S. Pat. No. 2,797,213, incorporated herein by reference. Other positive-working diazo compounds have been used for specific purposes. For example, a diazo compound used as a positive-working photoresist for deep U.V. lithography is Meldrum's diazo and its analogs is described by Clecak et al., "Technical Disclosure Bulletin," Volume 24, No. 4, Sep. 1981, IBM Corporation, pp. 1907 and 1908, and o-quinone diazide compounds suitable for laser imaging as shown in U.S. Pat. No. 4,207,107. The aforesaid references are also incorporated herein by reference.
The resin binders most frequently used with the o-quinone diazides in commercial practice are the alkali-soluble phenol formaldehyde resins known as the novolak resins. Photoresists using such polymers are illustrated in U.K. Patent No. 1,110,017, incorporated herein by reference. These materials are the product of reaction of a phenol with formaldehyde, or a formaldehyde precursor, under conditions whereby a thermoplastic polymer is formed.
In the prior art, the above-described positive photoresists using novolak resins as binders are most often used as a mask to protect substrates from chemical etching and photo-engraving processes. For example, in a conventional process for the manufacture of printed circuit boards, a copper clad substrate is coated with a layer of a positive-working photoresist, exposed to actinic radiation to form a latent circuit image in the photoresist coating, developed with a liquid developer to form a relief image, and etched with a chemical etchant whereby unwanted copper is removed and copper protected by the photoresist mask is left behind in a circuit pattern. For the manufacture of printed circuit boards, the photoresist must possess chemical resistance, must adhere to the circuit board substrate, and for high density circuits, must be capable of fine-line image resolution.
Similar photoresists are also used in the fabrication of semiconductors. As in the manufacture of printed circuits, the photoresist is coated onto the surface of a semiconductor wafer and then imaged and developed. Following development, the wafer is typically etched with an etchant whereby the portions of the wafer bared by the development of the photoresist are dissolved while the portions of the wafer coated with photoresist are protected, thereby defining a circuit pattern. For use in the manufacture of a semiconductor, the photoresist must possess resistance to chemical etchants, must adhere to the surface of the semiconductor wafer, and must be capable of very fine-line image resolution.
Recent developments in photoresist technology involve processes where high temperatures are encountered. For example, a recent development in the fabrication of semiconductors substitutes dry plasma etching for wet chemical etching to define a circuit. Plasma etching provides advantages over wet chemical etching in that it offers process simplification and improves dimensional resolution and tolerance. However, the demands on the photoresists are significantly greater when using plasma etching. For both wet etching and plasma etching, the photoresist must adhere to the substrate and must be capable of fine-line image resolution. For plasma etching, in addition to these properties, the photoresist must often be capable of withstanding high temperatures without image deformation and without eroding as plasma etching generates high temperatures at the wafer's surface.
The above-described prior art positive-working photoresists provide good resistance to chemical etchants and fine-line image resolution. However, they possess a relatively low glass transition temperature and soften and begin to flow at temperatures of approximately 120.degree. C. thereby resulting in image distortion and poor image resolution.
Various methods have been used in the prior art to increase the thermal performance of positive-working photoresists. For example, attempts have been made to increase the molecular weight of the novolak resins by chain extension, incorporation of di- and tri-alkyl substituted phenols and by use of higher molecular weight phenolic reactants. One method reported in the prior art involves increasing the aromatic content of the novolaks by replacing formaldehyde or other alkyl aldehydes used to form novolak resins with an aromatic aldehyde such as benzaldehyde. The substitution of benzaldehyde for formaldehyde is suggested by Hiraoka et al., "Functionally Substituted Novolak Resins, Lithographic Applications, Radiation Chemistry, and Photooxidation," Polymer Press (American Chemical Society, Division of Polymer Chemistry), Volume 25, No. 1, 1984, pp. 322-323. An additional method reported in U.S. Pat. No. 5,266,440 involves the use of resin blends or resin additives where one component of the blend has a high glass transition temperature.
Initial attempts to substitute aromatic aldehydes for aliphatic aldehydes were relatively unsuccessful because the aromatic aldehydes are substantially less reactive than the aliphatic aldehydes. Consequently, the resins formed by the substitution were relatively low molecular weight oligomers having softening temperatures comparable to those resins formed with aliphatic aldehydes. Relatively higher molecular weight aromatic novolak resins are disclosed in U.S. Pat. Nos. 5,216,111 and 5,238,776, incorporated herein by reference. In accordance with the procedures set forth in U.S. Pat. No. 5,238,776, a first aromatic novolak resin is formed by the condensation of a bis-hydroxymethyl phenol with another reactive phenol in the absence of an aldehyde to form an alternating novolak copolymer. In accordance with the procedures of U.S. Pat. No. 5,216,111, a phenol is reacted with an aromatic aldehyde to produce a novolak resin. The aromatic novolak resins produced by either patent can then be chain extended to increase molecular weight and thermal properties by further reaction with an aldehyde which may be an aliphatic or aromatic aldehyde to form a block copolymer; or by reaction with an aldehyde which may be an aliphatic or aromatic aldehyde with another phenol to form a block copolymer; or by reaction with a bis-hydroxymethylated phenol alone or in combination with an additional reactive phenol. The polymers formed by the reactions described in said patents have glass transition temperatures well in excess of the conventional novolak resins formed by reaction of a phenol with an aliphatic aldehyde.
In addition to those efforts directed towards increasing glass transition temperature of novolak resins by increasing their aromatic content, efforts have also been made to provide single component photoresists by combination of the photoactive component of the photoresist with the resin component by esterification of an o-quinone diazide sulfonyl compound with the phenolic hydroxyl group of the novolak resin. An early patent showing this reaction is U.S. Pat. No. 3,046,120, granted Jul. 24, 1962, where an o-cresol formaldehyde resin is esterified with a naphthoquinone-(1,2)-diazide-(2)-5-sulfonyl chloride. The resulting product was used for fabrication of printing plates. Additional efforts to combine a photoactive compound with a phenolic resin are reported in U.S. Pat. Nos. 3,635,709; 4,123,279; and 4,306,011, each incorporated herein by reference.
It is believed that the photoresist compositions described in each of the above patents have not been fully suitable for current submicron resolution (&lt;1.0 .mu.m) requirements. It is further believed that the reason that such photoresists are not fully suitable for commercial use is that photolithographic and other properties of the photoresist are compromised by both the selection of the resin structure and its subsequent esterification with the photoactive compound. For example, the esterification reaction consumes phenolic hydroxyl groups on the resin which groups are necessary for development of a photoresist coating. Therefore, when the hydroxyl groups are consumed, developability of the photoresist coating is compromised unless exposure energy is increased substantially to yield sufficient acidic groups to enable dissolution. Using such materials, residue-free development is difficult.
A recent effort to formulate a photoresist comprising the esterification product of a phenolic resin and an o-quinone diazide sulfonyl compound is disclosed in U.S. Pat. No. 5,279,918, granted Jan. 18, 1994, and incorporated herein by reference. The object of this patent is to provide a photoresist composition having resolution higher than conventional photoresists, a "practical sensitivity" and an image having a good pattern profile. This is achieved by condensing o-quinone diazide sulfonyl compound groups with relatively low molecular weight novolak resins with from 40 to 90 percent of the phenolic hydroxyl groups condensed with the o-quinone diazide sulfonyl group. It is believed that the objects of higher resolution and enhanced pattern profile are achieved because of the high concentration of o-quinone diazide units on the novolak resin backbone. However, a high concentration of the o-quinone diazide units substantially increases the cost of the photoresist. Moreover, it is further believed that low molecular weight novolak resins are required to enable development following exposure at a commercially acceptable energy dose because of the substantial number of phenolic hydroxyl groups esterified with the o-quinone diazide sulfonyl halide. This is shown by the experimental data given that "practical sensitivity" as a stated object of the patent means a substantially higher exposure dose than required for conventional photoresists to obtain clean development.